Treating hydrocarbon oils



United States Patent TREATING HYDROCARBON OILS Chyn Duog Shiah, 189 Nassau Ave., Manhasset, N.Y. No Drawing. Filed Feb. 6, 1957, Ser. No. 638,477

11 Claims. (Cl. 208-226) This invention relates to the treatment of hydrocarbon oils to remove undesired constituents therefrom and is more particularly concerned with a process for treating hydrocarbon oils which employs treating agents which are converted into a form suitable for use as intermediate materials in subsequent processing operations.

The purification of hydrocarbon oil stocks by removal of undesirable constituents is an ever-present problem in the petroleum refining industry and many processes have been proposed. The removal of various constituents from the hydrocarbon oil not only increases-the value of the oil but makes it more useful and in some cases easier to handle. For example, low sulfur crude oils always command a greater price than high sulfur crude oils. Similarly, low gravity or heavy crude oils always command a lower market value than lighter crudes. But, almost without exception, heavy, asphaltic crudes usually also have a high sulfur content. .The conventional commercial treatment for these types of crude oil is coking. Coking, however, usually yields a coke which represents about 10- 25% by weight of the oil and the coker oil is only about 65-75% by weight. The coke usually carries with it about of the sulfur in the oil charge. Thus, the oil produced still has a sulfur content only slightly lower than the original, whereas the coke produced contains such a high percentage of sulfur that it is ditficult to find a marketfor it.

As a typical example, a 6 API reduced Kuwait crude containing 5.37% by weight sulfur when subjected to coking at 500 C. yields 74.1% by weight of oil which still contains 4.l2% by weight sulfur. The coke yield is 18.5% by weight butit contains 10.1% by weight sulfur (D. C. Jones et al., Industrial and Engineering Chemistry, vol. 46, pages 12-15, 1954). I

i It is an object of the present invention to provide an improved process for treating hydrocarbon oils to remove therefrom undesired constituents such as asphaltic materials, sulfur compounds, metallic components, oxygen bodies, nitrogen bodies, and the like. i

It is another object of the invention to provide a process ofthecharacter indicated which involves the use of a treating agent which is removed from the process as a by-product which is utilizable as an intermediate in a chemical processing operation normally employing the treating agent per se.

It is a further object of the invention to provide a process of treating hydrocarbon oils which is effective to remove undesired constituents from said oils and simultaneously to produce a by-product readily convertible into cement clinker.

It is a feature of the invention that not only is a puri-. fied hydrocarbon oil produced but there is also produced a valuable and useful by-product.

It is another feature of the invention that the hydrocarbon treating process may be combined with other chemical conversion operations to form an integrated operation providing high efiiciency in heat and raw material consumpt on. I 1 i it Other objects and features of the invention will be readity apparent from the following detailed description of the invention with particular reference to illustrative embodiments.

In accordance with the invention, the hydrocarbon oil stock to be treated, such as a heavy hydrocarbon crude containing substantial quantities of asphaltic constituents, sulfur bodies, metallic compounds, oxygen bodies, nitrogen bodies or the like is brought into contact with a treating agent or catalyst which is a metallic oxide, a silicon oxide or a metal salt of phosphoric acid, sulfuric acid or carbonic acid, or a mixture of such compounds in various proportions. The oil and treating agent are reacted at temperatures of 500 to 1200 F. and the percentage of treating agent employed is generally 1 to 250%, preferably 20 to based upon the weight of the oil. The greater the percentage of undesired constituents in the oil, the greater the percentage of treating agent. The amount of treating agent used is adjusted so that the undesirable constituents taken from the oil and intimately intermixed with the agent shall be in the right proportions to best enhance the value of the agent as a raw material for further processing into other useful product or products. After treatment, which may range from 0.5 to 65 minutes in length, the reaction product of the treating agent with the undesired constituents, which may be a physical or a chemical combination, is separated from the treated oil by vaporization, filtering, decantation, centrifuging or other like separating means and the separated reaction product is then employed as raw material for a chemical conversion process which normally employs the original treating agent as its main raw material. A typical example would be a mixture of lime or limestone and clay in suitable proportions. This mixture is reacted with the oil. The clay enhances the decomposition of the The lime reacts with sulfur and other undesirable acidic elements in the oil. Thus, we obtain a high yield of on with much improved quality and simultaneously obtain an intimate mixture of lime, clay, coke and sulfur. Upon burning the mixture with air and/ or oxygen at 1300 C., cement clinker is formed. As is well known, fuel is the single most expensive component in the manufacture of cement. In accordance with the process of this invention fuel is being provided in situ and the fuel thus provided is an otherwise almost worthless and burdensome by-product of petroleum processing. Since the fuel is in intimate ad mixture and/or combination with the reactants being burned to form the clinker, the heat generated by its combustion is, in essence, generated from within. Therefore. the rate of reaction is greatly accelerated and the yield loss is reduced. Whatever sulfur has been removed from the oil will appear as sulfur dioxide upon burning of the clay-lime-coke mixture. The sulfur dioxide can be further processed into sulfuric acid or elemental sulfur. The amount of lime and/ or limestone and clay used is readily determined by the extent of the quality improvement of the oil desired, and the amount of carbon and sulfur removed may or may not, be the exact amount required in the subsequent reaction. The process of this invention therefore simultaneously effects Deasphalting or decoking of the oil,

Desulfurization of the oil,

General improvement of the oil, and

Production of fuel and/or other reactant for further chemical processing.

about 500C. and therheat of cracking of the oil can at least partially be supplied by the flue gas from the cement clinker manufacture.

While lime or limestone and clay have been referred to above as suitable treating agents, various other normally solid oxides or metal salts, used either alone or in admixture, are suitably employed in accordance with this-invention.- Examples of such other treating agents are calcium oxide, aluminum oxide, titanium oxide,-magnesiumoxide, iron oxide, silicon oxide, calciumphosphate, sodium sulfate and sodium carbonate. In general, I contemplate the-use of oxides of elements of groups IA, IIA, III-A, IVA, IVB and VIII of the periodic table or salts of these elements with phosphoric acid, sulfuric acid, or carbonic acid. The following specific examples will'serve to illustrate further the'features of the process of the invention, it being understood thatthese examples are illustrative only and do not limit the scope of the invention, all parts being by weight.

The process of this invention is applicable toand effective upon a wide variety of hydrocarbon oils such as crude oil, gasoline, kerosene, diesel oil, lubricating oil stocks, charging stock of petroleum origin for catalytic crackers, coal-tar and coal-tar distillates, liquid petroleum-like products from the hydrogenation of solid fuels such as coal, shale oil and shale oil distillates, oil from tar sands, other. synthetic liquid fuel products and the like. The foregoing list of products to which the invention is applicable is illustrative only and other bydrocarbon oil materials may be effectively treated in accordance with my invention.

The invention is particularly suitable for heavy petroleum oils having a specific gravity of 0.8 or more and to oils'having a sulfur content of 1% by Weight or more and/or acontent of asphaltic constituents as measured by a Conradson carbon residue of 1% or more. In accordance with my process the specific gravity is reduced by at least 8 API, the sulfur content is reduced by at least 40%v and the Conradson carbon residue is reduced by at least 50%.

Example I To 100 parts of a 10 API heavy Mexican Bunker fuel oil containing 4.4% sulfur and having a Conradson carbon residue of 13.5% is added 43.8-parts of calcium oxide and 23.6 parts of filtrol clay. The mixture is heated to 500 C. for 60 minutes. The solid reactant phase is separated from the oil phase by vaporization. A straw colored light oil with aspecific gravity of 0.876, representing 75% of the oil charged, is recovered. The sulfur content of the oil is 2.79%. Thus 53% of the sulfur in the oil is removed by the calcium oxide-clay mixture. The solid phase represents 78.5 parts and is in the form of a grayish black loose powder containing the lime and clay originally charged. This mixture is heated to 500 C., and reacted with a stream ofoxygen for 30 minutes. rises to about 1300 C. and atypical grayish colored'cement clinker is produced. The gas and lossesof the operation are 6.2% by weight of the oil treated.

Example 11 A blast furnace slag (50 parts) with the following analysis is used with 25 parts of calcium oxide for thetreatment of 100 parts of the oil described in Example I. A light oil, 28.6' API, representing 75% by weight of the crude charged, is obtained. Thesulfur. content of the purified The temperature of the reaction mass oil is 2.35%. The weight percent of sulfur removed from the oil charge is 52.3%. The mixture of slag and lime plus coke and other impurities removed from the oil is processed into a cement clinker as described in Example I.

While the used treating agent obtained from the above examples is, as described, further processed to manufacture cement, it will be'understood that the used treating agent may also be employed in other chemical conversions which normally employ the original treating agent as a raw material. For example, when calcium oxide is used as the treating agent, the by-product containing calcium oxide which is'separated from the treated oil is readily converted to calcium carbide in accordance with conventional industrial operating procedures. Similarly, used sodium sulfate is further processed to sodium sulfide, used sodium carbonate is converted to sodium cyanide, used aluminum oxide is converted to aluminum chloride, used titanium oxide is reacted to form titanium tetrachloride, used magnesium oxide-is further treated to form magnesium" chloride, used iron oxide is further processed to form pig iron, used silicon oxide is converted into silicon carbide, and used calcium phosphate is treated to form elemental phosphorus.

It will be understood that all of the above subsequent conversions of the used treating agent are carried out in accordance with conventional procedures. For example, typical commercial operations involving the abovementioned compounds which are used as treating agents in accordance with this invention, employ the reactions ily apparent from the following detailed description of the In accordance with the invention, therefore, there is provided a process which has important technological and economical advantages since it produces no waste materials and the treating agents rather than being consumed or converted into a form which requires recovery or regeneration before further use, are converted into a form whichcan be immediately used'to advantage in chemical operations which normally employ the treating agent as a raw material, the use of the treating agent in the oil treating process of the invention having benefited the treating agent from the standpoint of .its later use. The oil treated has thus. been-purified and sep-' aratedfrom. undesired constituents by means of a reagent which involves no cost to the-oil treating opera-. tion.

In effect, raw materials used inestablished chemical industries, such as the cement industry, are caused to make a detour through a petroleum refining operation before being, used for cement production or other conversion, a detour which is of substantial economic value to both operations, in which the raw'materials are employed.

It will be obvious to those'skilled in the art that various changes and modifications may be made in the process herein described and illustrated by specific examples without departing from the spirit and scope of the invention as defined in the appended claims and it is intended, therefore, that all matter contained in the foregoing de scription shall beinterpreted as illustrative only and not as limitative of the invention.

What I claim and desire to secure by Letters Patent is:

1. A process of treating-a hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which purified oil phase and a used reagent phase containing said compound combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase.

2. A process of treating a hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide and clay to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase.

3. A process of treating a hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide and clay to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase and oxidizing said reagent phase to form cement clinker.

4. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with 1% to 250% by weight of at least one compound selected from the group consisting of normally-solid oxides at a temperature of 250 to 550 C. to produce a purified oil phase and a used reagent phase containing said compound combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase.

5. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase With 1% to 250% by weight of calcium oxide and clay in various proportions at a temperature of 250 to 550 C. to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase.

6. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodiesfrom said oil which comprises bringing said oil into contact in the liquid phase with 1% to 250% by weight of calcium oxide and clay in various proportions at a temperature of,250 to 550 C. to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase and oxidizing said reagent phase to form cement clinker.

7. A process of treating a heavy hydrocarbon oil having asubstantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide, at least one other oxide selected fromthe group consisting of silicon oxide, aluminum oxide, magnesium oxide and iron oxide to produce a purified oil phase and a used reagent phase containing said oxides combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase.

8. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide and at least one other oxide selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide and iron oxide to produce a purified oil phase and a used reagent phase containing said oxides combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase, and oxidizing said reagent phase to form cement clinker.

9. A process of treating a hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide and clay to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase, said reagent phase being oxidizable to form cement clinker.

10. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with 1% to 250% by weight of calcium oxide and clay in various proportions at a temperature of 250 to 550 C. to produce a purified oil phase and a used reagent phase containing said calcium oxide and clay combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase, said reagent phase being oxidizable to form cement clinker.

11. A process of treating a heavy hydrocarbon oil having a substantial content of asphaltic constituents, sulfur bodies and the like to separate at least a portion of said asphaltic constituents and sulfur bodies from said oil which comprises bringing said oil into contact in the liquid phase with calcium oxide and at least one other oxide selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide and iron oxide to produce a purified oil phase and a used reagent phase containing said oxides combined with said portion of said asphaltic constituents and sulfur bodies, and separating said used reagent phase from said purified oil phase, said reagent phase being oxidizable to form cement clinker.

References Cited in the file of this patent Great Britain Sept. 9, 1927 

1. A PROCESS OF TREATINGA A HYDROCARBON OIL HAVING A SUBSTANTIAL CONTENT OF ASPHALTIC CONSTITUENTS, SULFUR BODIES AND THE LIKE TO SEPARATE AT LEAST A PORTION OF SAID ASPHALTIC CONSTITUENTS AND SULFUR BODIES FROM SAID OIL WHICH COMPRISES BRING SAID OIL INTO CONTACCT IN THE LIQUID PHASE WITH AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF NORMALLY-SOLID OXIDES TO PRODUCE A PURIFIED OIL PHASE AND A USED REAGENT PHASE CONTAINING SAID COMPOUND COMBINED WITH SAID PORTION OF SAID ASPHALTIC CONSTITUENTS AND SULPHUR BODIES, AND SEPARATING SAID USED REAGENT PHASE FROM SAID PURIFIED OIL PHASE. 